Yarn treating



Patented June 16, 1942 UNITED STATES PATENT OFFICE 2,286,824 YARN TREATING.

James G. McNally and Joseph B. Dickey, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester,-N. Y., a corporation of New Jersey No Drawing. Application November 26, 1937, Serial N0. 136,693

11 Claims.

This invention relates to the treatment of yarns, and more particularly to a method of conditioning yarns composed of or containing organic derivatives of cellulose, such as cellulose acetate, by means of the dioxane ethers, to render them free from such undesirable properties as high friction, static electrification, scroop and harsh feel. The invention also relates specifically to the preparation and use as yarn lubricants of hitherto unknown dioxane ethers of higher aliphatic alcohols.

As is well-known, in the manufacture of yarns,

particularly those composed of or containing organic derivatives of cellulose, it is necessary to treat the yarn in order to reduce the tendency towards breakage of the individual filaments or fibers when they are subjected to various mechanical strains and to lubricate the yarn in order to facilitate the handling in such operations such as spinning, twisting, winding and reeling. It is also necessary to treat yarn to adapt it for use as warp or filling in the manufacture of various types of knitted fabrics. Furthermore, it is customary to treat yarn to improve its scroop and to reduce and minimize-its harsh feel.

This invention has as its principal object to or alcoholates and chlorinated dioxane. The general reaction is illustrated in the Journal of the American Chemical Society, vol. 55, page 1284, in which article dioxane ethers of ethyl alcohol and of benzyl alcohol are described. Included among the new compounds we have prepared and found useful as ingredients of yarn treating compositions are dioxane ethers derivable from cyclohexanol, from the monoethyl ether of ethylene glycol and from tetrahydrofurfuryl alcohol.

The discovery that the higher alkyl ethers of dioxane may function as lubricants for cellulose derivative materials is wholly unexpected and unpredictable from prior knowledge of the characteristics of dioxane or dioxane ethers of lower alcohols. In accordance with our invention these compounds may be applied directly to the yarn during or after spinning, or may be added to the provide an entirely new class of yarn conditioning agents which are particularly adapted for the treatment of yarns composed'of or containing organic derivatives of cellulose and capable of lubricating, softening and rendering such yarns more amenable to various textile operations including weaving, knitting and the like. A fur-.

ther object is to provide a class of conditioning agents which augment or assist the lu ricating action of various standard yarn lubrican when applied to cellulose derivative yarns. A still further object is to provide a yarn lubricating composition which can be readily removed from the Reaction products of 2-3 di-chloro 1-4 dioxane yarns by the usual scour baths. Another object is to provide a new class of hitherto unknown chemical compounds. Other objects will appear hereinafter.

These objects are accomplished by the following invention which involves the use in yarn lubricating formulas of the dioxane ethers and more particularly certain hitherto unknown compounds, namely, the dioxane ethers of higher.

aliphatic monohydric and certain polyhydric alcohols. These compounds, the preparation. of which will be described in detail hereinafter, may be prepared by the interaction between alcohols and cyclohezanol 200 gms. (2 mols) of cyclohexanol were heated with 157 gms. (1 mol) of 2-3 di-chlorodioxane. After the reaction was started it continued with the evolution of heat. Heating was continued about 3 hrs. The reddish brown reaction mixture was distilled in a. high vacuum. The boiling range indicated the presenceof at least four compounds. The product may be regarded to have the following structural formula:

The fraction boiling from 165 to 215 C./3 mm. is useful as a dressing or lubricant for yarn or fllms.

Ethers derived from 22-3 chloro 1-4 dioxane and the monoethyl ether of ethylene glycol The portion boiling between 164-,184 C./3 mm., a water white oilyvliquid, had good lubricating qualities. The ether prepared in a similar manner from p-methoxy-ethanol boils at l50-180 C./18 mm. and from p-ethoxy-p-ethoxy ethanol 165-190 C./4 mm.

1-4 dioxane 2-3 di-Z auryl ether Three hundred sixty-eight grams (2 mols) of a technical grade of lauryl alcohol were placed in a 1-liter flask with 157 grams (1 mol) of 2-3 dichlorodioxane. The flask was then equipped with an inverted Liebig condenser attached to a hydrogen chloride trap and heated with a free flame to 100. A reaction began as was evidenced by the rapid evolution of hydrogen chloride. Heating was continued at 100-150 C. for two hours and then slowly raised to 160-165, at which temperature it was kept for two hours. The brown reaction product was then fractionated under reduced pressure from a 1-liter distilling flask. The product, boiling at 220-280/9 mm., was taken to be the desired ether, The product thus obtained has a light yellow color and is an excellent yarn lubricant.

1-4 dioxane 2-3 di-cetyl ether Two thousand four hundred twenty gms. (10 mols) of a technical grade of cetyl alcohol were placed in a -liter flask with 785 gms. (5 mols) of 2-3 dioxane dichloride. The flask was then equipped with an inverted Liebig condenser, attached to a hydrogen chloride trap, and warmed with a free flame to 110-116 for 3 hrs. and then the temperature was slowly raised to 1'70-1'75 and kept at that temperature for 3 hours. The brown reaction product was then distilled under reduced pressure from a 5-liter flask with water cooled side arm receiver. The product thus obtained has a light yellow color and is an excellent yarn lubricant.

- two hours.

i4 dioxane Z-3 ditetrahydrojurluryl ether 0 one-om mo o-o-om- H mcur-on,

One hundred two grams (1 mol) of tetrahydrofurfuryl alcohol and 78.5 grams (0.5 mol) of 2-3 dichloro-dioxane are heated in a 250 cc. flask under a reflux condenser to 90. Hydrogen chloride was evolved in the reaction mixture which turned black. The temperature was slowly raised to 115-120 and kept at that temperature for The product was then fractionated under reduced pressure. The fraction boiling at 208-230/16 mm. was taken to be the desired ether. The product has a light yellow color, is slightly viscous and is slightly slippery when pressed between the flngers.

1-4 dioxane 2-3 dimethyl ether Thirty-one and four tenths grams (0.2 mol) of 2-3 dichloro-dioxane and 62.4 grams (0.4 mol) of menthol were heated together in a 250 cc. flask in an oil bath heated to l20-l30 for three hours and then at 150-160 for 1 hour. Hydrogen chloride practically -ceased to be evolved at the end of the time given. The dark-brown reaction mixture was then fractionated under reduced pressure and after the removal of some unchanged menthol (5g.) and a low boiling fraction there were obtained 26 g. of a very viscous material boiling at 220-265/ 10 mm. This material was then crystallized from methanol and '7 g. of a white crystalline material were obtained, melting at 141-l46. The alcoholic residue upon distillation under reduced pressure yielded 15.8 g. of a compound boiling at 210-250/ 10 mm. This material is light yellow in color, slightl viscous and is a good lubricant.

1-4 dioxane 2-3 di-n-but'yl ether Two hundred g. (2.7 mols) of n-butyl alcohol and 204 g. (1.3 mols) of 2-3 dichloro dioxane Example I Yarn designed for weaving and composed of cellulose acetate is treated by applying thereto by means of an applicator roll a mixture having the following composition:

. Parts Dioxane di-cetyl ether 30 Olive oil 60 Sulfonated castor oil 10 The amount of the composition applied is sufflcient to give a lubricant content of the yarn of about 2 /2%,

Example II The yam conditioning liquid is made up by mixing the following ingredients in the indicated proportions:

Parts Dioxane di-lauryl ether 20 Blown olive oi 20 Mineral oil- 20 Sulfonated lauryl alcohol 9.5 Triethanolamine 0.5

This composition is applied to a cellulose acetate yarn intended for weaving in an amount suflicient to leave on the yarn a lubricant deposit of 2-5%, based on the weight of the untreated yarn. The yarn so treated is found to be soft and relatively pliable and substantially free from a tendency from the accumulation of static electrical charges under frictional influences.

Other examples of yarn-conditioning compositions which may be appliedin accordance with our invention to various types of yarn, particularly those composed of or containing cellulose acetate, cellulose propionate, cellulose acetate propionate, cellulose acetate butyrate and similar cellulose organic derivatives and which renders such yarns particularly amenable to weaving, are the following which are applied in such manner asto leave a deposit of about 2% of the composi- 1,4-dioxane 2-3 di-ether of mono-ethyl ether of ethylene glycol 20 Olive oil 30 Triethanolamine 2 Oleic acid Other examples of compositions adapted in accordance with our invention for the treatment of yarns composed of or containing organic derivatives of cellulose and the like to adapt them for use as knitting yarns, are the following which are deposited in an amount representing about ill-%, based on the dry weight ofthe yarn.

Example V1 Parts Blown olive oil 30 Dioxane di-tetrahydrofurfuryl ether 6d Lauryl alcohol 10 ,Example Vll Parts Dioxane di-methyl ether 50 Castor oil 40 Diethylene glycol 10 Example VIII Parts 1,4 dioxane di-ether of ethylene glycol monomethyl ether Blown olive oil Still further examples of' yarn-conditioning agents prepared in accordance with our invention which may be applied to yarns composed of or containing cellulose derivatives such as cellulose acetate, in varying amounts and for various purposes, arethe following: 7

If the compositions of Examples IX, X, and XI are applied to yarn intended for weaving, they should be deposited in an amount representing about 2%-5% of the dry weight of the yarn. If the yarns are intended for knitting, the amount of the composition deposited should represent about 10-15%.

Of the above compositions, we have found that those of Example 1, characterized by the presence therein of dioxane di-cetyl ether, those of Examples II and III, by the presence therein of dioxane di-lauryl ether and those of Examples V, X, and XI, characterized by the presence therein of 1,4-dioxane-2,3-cli-ether of mono-ethyl of ethylene glycol, dioxane di-p-ethoxy-p-ethoxyethylether and dioxane di-fl-methoxyethylether respectively, are unique in their ability to reduce or eliminate accumulations of static electricity on yams of the type herein referred to, particularly when such yarns are employed for the manufacture of cut staple fibers. It is therefore one of the specific features of our invention to employ these compositions as anti-static agents generally, and specifically for the manufacture of cut staple yarns. In producing cut staple fibers, the

selected composition may be deposited on the fiber after the cutting operation in any convenient manner, as by a conventional type of applicator, or by spray, immersion or the like. Cut staple fibers treated in this manner display a very marked reduction in their tendency to accumulate charges of static electricity and in many cases this tendency is substantially or completely eliminated.

A will be apparent from the above examples and description, the conditioning agents of our invention may be applied by a wide variety of methods. For example, we may employ the agent as an ingredient of the spinning dope from which the filaments are formed, the amount of the agent so employed depending upon a number of factors, such as the particular cellulose derivative used in making the yarn, the solvent or solvent combination used in making up the spinning solution, and the degree of softness or pliability desired in the yarn, etc.

If the conditioning agent is to be applied to the yarn after spinning, this may be done by bringing the yarn in contact with a wick, roll, or felt wet therewith or the liquid may be applied by immersion, spray, or otherwise. The particular point at which the liquid is applied may vary. It may, for example, be applied to the yarn inside or outside the spinning cabinet, between the guide and godet roll, between the godet or other roll or guide and the point of winding and/or twisting. In some cases, the liquid may even be applied to the yarn after winding onto cones, spools, bobbins, or the like or by the so-called bobbin to bobbin method. In the case of staple fiber manufacture, the liquid may be applied to the yarn prior to, or after cutting into staple lengths.

The amount of the agent 50 employed will vary widely depending upon the results desired, the specific nature of the material to which the agent is applied, the use to which the yarn is eventually to be put and other factors. For example, in a given case where a cellulose organic acid ester yarn such as a yarn composed of cellulose acetate, is intended for knitting, about 10-45% or more by weight, based on the weight of the dry yarn, may be satisfactory, while if the yarn is intended for weaving, the amount may vary between about 2 and 5%.

Although in the above examples we have referred primarily to yarn treating compositions containing only the conditioning agent and an oil, other ingredients such as solvents, non-solvents, emulsifying agents, blending agents and the like, may be added within the scope of our invention. Likewise, various dyes or other coloring matter may be included in case it is desired to permanently or fugitively tint or dye the material undergoing treatment.

Although we have found it convenient to illustrate our invention by reference to compositions containing specific percentages of the various ingredients, these percentages may vary widely depending upon the particular purpose for which the composition is intended. For example, if it is desired to control the solvent or softening action of the conditioning agent, the amount of the agent may be adjusted as, for example, by reducing the amount of the agent and correspondingly increasing the amount of oil or other ingredient.

While we have described our invention with particular reference to the treatment of yarns composed of organic derivatives of cellulose such as cellulose acetate, the conditioning agents and formulas described herein are applicable to the conditioning of many other types of cellulose derivative yarns such a those composed of or containing cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, ethyl cellulose, methyl cellulose, benzyl cellulose and others, as well as to the conditioning of silk, wool, cotton, viscose and other natural or artificial materials.

The term yarn as used herein in the cla'ms is to be understood as including a single filament, a plurality of filaments associated into the form of a thread, either of high or low twist, single or multiple threads associated or twisted together, composite threads composed of a mixture of natural and artificial filaments or a composite thread formed by twisting together individual strands of natural or artificial materials, as well as cut staple fibers produced from natural and/or artificial filaments or threads and spun yarn produced from such staple fibers.

We particularly wish to point out that the dioxane di-ethers derived in accordance with our invention from the higher alcohol such as cetyl,

lauryl, and cyclohexyl, as well as the dioxane diethers derived from alkoxy compounds and from tetrahydrofurfuryl alcohol are new chemical compounds and so far as we are aware have never heretofore been prepared. Obviously, such compounds have never been applied to synthetic yarns to condition them for use in various textile processes. The broad scope of our invention, however, includes the use of any of the dioxane di-ethers as yarn-conditioning agents. Specifically, the di-cetyl, di-lauryl, di-cyclohexyl and di-tetrahydrofurfuryl ethers as well as those derived from the monomethyl and monoethyl ethers of ethylene glycol, we claim as new chemical compounds.

What we claim is:

1. The process of conditioning yarn composed of or containing organic derivatives of cellulose to render it more amenable to textile operations including knitting, weaving, spinning and the like which comprises applying thereto a lubricating composition containing a l-4 dioxane-2-3 dialkyl ether.

2. The process of conditioning yarn composed of or containing organic derivatives of cellulose to render it more amenable to textile operations including knitting, weaving, spinning, and the like which comprises applying thereto a lubricating composition containing a 1-4 dioxane-2-3 dialkyl ether in which each ether group contains at least six carbon atoms.

3. The process of conditioning yarn composed of or containing organic derivatives of cellulose to render it more amenable to textile operations including knitting, weaving, spinning and the like which comprises applying thereto a lubricating composition containing a dioxane dicetyl ether.

4. The process of conditioning yarn composed of or containing organic derivatives of cellulose to render it more amenable to textile operations including knitting, weaving, spinning, and the like which comprises applying thereto a lubricating composition containing a dioxane di-lauryl ether.

5. The process of conditioning yarn composed of or containing organic derivatives of cellulose to render it more amenable to textile operations including knitting, weaving, spinning, and the like which comprises applying thereto a lubricating composition containing a dioxane di-cyclohexyl ether.

6. The method of reducing or eliminating the tendency of cellulose derivative cut staple fibers to accumulate charges of static electricity, which comprises treating the fibers with an antistatic agent selected from the group consisting of dioxane di-cetyl ether, dioxane di-lauryl ether, dioxane dicyclohexyl ether, 1,4-dioxane-2,3-diether of the mono-ethyl ether of ethylene glycol, dioxane di-B-ethoxy-fi-ethoxyethylether and dioxane di-fi-methoxyethylether the ether groups of each of said compounds being attached to the 2,3 carbon atoms of the dioxane nucleus.

'7. Textile yarns composed of or containing organic derivatives of cellulose and amenable to textile operations including knitting, weaving, spinning and the like impregnated with a lubricating and conditioning agent containing a 1-4 dioxane 2-3 dialkyl ether.

8. Textile yarns composed of or containing organic derivatives of cellulose and amenable to textile operations including knitting, weaving, spinning, and the like impregnated with a lubricating and conditioning agent containing a l-4 dioxane 2-3 dialkyl ether in which each ether group contains at least six carbon atoms.

9. Textile yarns composed of or containing organic derivatives of cellulose and amenable to textile operations including knitting, weaving, spinning, and the like impregnated with a lubricating and conditioning agent containing a dioxane dicetyl ether.

10. Textile yarns composed of or containing organic derivatives of cellulose and amenable to textile operations including knitting, weaving,

spinning and the like impregnated with a lubricating and conditioning agent containing a dioxane dilauryl ether.

11. Textil yarns composed of or containing organic derivatives of cellulose and amenable to textile opeigitions including knitting, weaving, spirming, and the like impregnated with a lubricating and conditioning agent containing a dioxane dicyclohexyl ether.

JAMES G. McNALLY. JOSEPH B. DICKEY. 

